Correlating structural distributions in silica glass with two-dimensional $J$-resolved spectroscopy

Abstract

A two-dimensional (2D) $J$-resolved magic-angle spinning nuclear magnetic resonance (NMR) spectrum of silica glass at $^{29}$Si natural abundance levels, 4.7%, was measured using the shifted-echo phase-incremented echo train acquisition (SE-PIETA) pulse sequence. At $^{29}$Si natural abundance levels the $J_\text{Si-O-Si}$ coupling splittings appear as overlapping doublet patterns arising from isolated $^{29}$Si−O−$^{29}$Si linkages. The experimental 2D J-resolved spectrum is analyzed to obtain a bivariate probability distribution correlating the central Si-O-Si angle of a Q4−Q4 linkage to its mean Si-O-Si angle (seven angles) using relationships between $^{29}$Si isotropic chemical shifts and geminal $J$ SiO-Si coupling of a Q4−Q4 to its local structure. To obtain a self-consistent bivariate probability distribution it was necessary to introduce an additional dependence of the $^{29}$Si chemical shift of a Q4 on mean Si-O distance as well as mean Si-O-Si angle. The implication of this necessary modification is a positive correlation between Si-O-Si angle and Si-O distance in the silica glass, consistent with recent $^{17}$O NMR measurements on ambient and densified silica glasses but running opposite to the trend generally found in crystalline silica polymorphs. From the analysis of the $^{29}$Si 2D J-resolved spectrum we determine a Si-O-Si bond angle distribution in silica glass as having a mean at $147.8^\circ$, a mode at $147^\circ$, and a standard deviation of $10.7^\circ$. Our statistical model for analyzing the experimental $^{29}$Si 2D $J$-resolved spectrum also indicates that the individual Si-O-Si bond angle distributions are relatively uncorrelated.

Publication
Physical Review B